Defect Chemistry, Sodium Diffusion and Doping Behaviour in NaFeO Polymorphs as Cathode Materials for Na-Ion Batteries: A Computational Study.

Minor metal-free sodium iron dioxide, NaFeO, is a promising cathode material in sodium-ion batteries. Computational simulations based on the classical potentials were used to study the defects, sodium diffusion paths and cation doping behaviour in the α- and β-NaFeO polymorphs. The present simulations show good reproduction of both α- and β-NaFeO. The most thermodynamically favourable defect is Na Frenkel, whereas the second most favourable defect is the cation antisite, in which Na and Fe exchange their positions. The migration energies suggest that there is a very small difference in intrinsic Na mobility between the two polymorphs but their migration paths are completely different. A variety of aliovalent and isovalent dopants were examined. Subvalent doping by Co and Zn on the Fe site is calculated to be energetically favourable in α- and β-NaFeO, respectively, suggesting the interstitial Na concentration can be increased by using this defect engineering strategy. Conversely, doping by Ge on Fe in α-NaFeO and Si (or Ge) on Fe in β-NaFeO is energetically favourable to introduce a high concentration of Na vacancies that act as vehicles for the vacancy-assisted Na diffusion in NaFeO. Electronic structure calculations by using density functional theory (DFT) reveal that favourable dopants lead to a reduction in the band gap.